Quaternary ammonium derivatives of indene

ABSTRACT

MICROBIOCIDAL QUATERNARY AMMONIUM DERIVATIVES OF INDENE, AT LEAST SOME OF WHICH RETAIN A HIGH DEGREE OF THEIR MICROBIOCIDAL ACTIVITY IN HARD WATER, THE QUATERNARY NITROGEN HAVING A LONG CHAIN ALKYL OF 8 TO 18 CARBON ATOMS, BUT PREFERABLY 12 TO 14 CARBON ATOMS, AND TWO LOWER ALKYL CHAINS OF 1 TO 4 CARBON ATOMS ATTACHED THERETO.

United States Patent 3,636,115 QUATERYARY AMMONIUM DERIVATIVES 0F INDENE Edward Griifin Shay, Belle Mead, and Edward A, Tavss,

Jersey City, N.J., assignors to Millmaster Onyx Corporation, New York, N.Y. No Drawing. Filed Sept. 12, 1969, Ser. No. 857,573 Int. Cl. C07c 87/6'8 US. Cl. 260567.6 M Claims ABSTRACT OF THE DISCLOSURE Microbiocidal quaternary ammonium derivatives of indene, at least some of which retain a high degree of their microbiocidal activity in hard water, the quaternary nitrogen having a long chain alkyl of 8 to 18 carbon atoms, but preferably 12 to 14 carbon atoms, and two lower alkyl chains of 1 to 4 carbon atoms attached thereto.

This invention relates to a new class of microbiocidally active quaternary ammonium compounds, and it partic ularly relates to quaternary ammonium compounds derived from indene.

Many quaternary ammonium compounds have heretofore been known which were very eifective microbiocidal agents. However, most of these prior compounds were found to lose a large part of their microbiocidal eifectiveness when subjected to dilution with hard water. The compounds of the present invention are quaternary ammonium derivatives of indene wherein the quaternary nitrogen has a long chain of 8 to 18 carbon atoms and also has twO lower alkyls of 1 to 4 carbon atoms attached thereto. These compounds are highly microbiocidal. Furthermore, those of these compounds which have a long chain of 12 to 14 carbon atoms have been found to be among the relatively few quaternaries which are not only highly microbiocidal but which are not deleteriously affected by hard water.

The term hard water is generally used to describe water having at least about 75 p.p.m. of calcium carbonate or equivalent salts. However, naturally occurring water may, and usually does contain such salts in an amount running up to several hundred p.p.m.

In accordance with the present invention, quaternary ammonium derivatives of indene may be prepared through hydrogenation, chloromethylation and reaction with tertiary amines as set forth in the following reaction:

CHzCl In the above reaction, R is an alkyl group of between 12 and 14 carbon atoms, while R and R are lower alkyls of 1 to 4 carbon atoms.

Indene is well known and widely used as a monomer for the preparation of commercial resins. -It occurs in the solvent naphtha cuts of coal tar distillates. It is, therefore,

3,636,115 Patented Jan. 18, 1972 ice 833 grams of crude indene (X-168 Heavy Solvent B. 172188 C.; Neville Chemical Company, Pittsburgh, Pa., 780 grams of methanol and 7.75 grams of palladiumcharcoal catalyst were placed in a hydrogenation vessel. Hydrogenation was accomplished in 8 hrs. at 130 C. at a pressure of about 60 p.s.i. with vigorous stirring. The vessel was cooled and the solution discharged and filtered to remove the catalyst. Methanol and forerun up to 170 C. were removed by distillation, and material boiling at 170-176 C. was taken as the product (650 grams). Although the pressure used here was 60 p.s.i., it has been found that a pressure as high as about 500 p.s.i. may be used with the same result.

EXAMPLE II To a stirred mixture containing 590 grams of indan from Example I, 507 cc. of 37% formaldehyde and 1060 cc. of cone. HCl, was added 695 cc. of conc. sulfuric acid over seven hours. The temperature was held at 60 C. for this period. Stirring was continued for twenty hours. The reaction mixture was then poured into ice-water and extracted with ethyl ether. The ether layer was washed twice with 5% sodium bicarbonate and once with water. It was then dried overnight over anhydrous sodium sulfate, filtered and then distilled.

Fractions having a boiling point of 120140 C. at 810 mm. Were combined to give 420 grams of chloromethyl indan.

EXAMPLE III Chloromethyl indan was reacted with several alkyl dimethyl amines, as follows:

Chloro- Chloro- Alkyl Alkyl methyl methyl dimethyl dimethyl indan, Indan, amine, amine,

Alkyl chain grams moles, grams moles nC 4. 9 0.03 5.6 0.03 nCn 4. 9 0.03 6. 6 0. 03 nCn 4. 9 0. 03 7. 7 0.03

The chloride and amine were weighed into a 50 m1. round bottom flask and an equal weight of isopropyl alcohol added. The mix was refluxed on a steam bath overnight giving 95% conversion to alkyl dimethyl indanylmethyl ammonium chloride in each case.

EXAMPLE IV The products of Example III were evaluated for hard water tolerance using the AOAC Gcrmicidal and Detergent Sanitizers test method procedure No. 5023 with E. coli ATCC #11229.

The results were as follows:

The Phenol Coefiicient for (2) vs. S. aureus was determined to be 830; vs. S. typhsa-780.

EXAMPLE V Reagent grade indan (99%), supplied by Aldrich Chemical Company, was chloromethylated using the conditions of Example II, and this chloromethyl indan was reacted with C and C alkyl diethyl amines and C and C alkyl dimethyl amines as described in Example III.

The products of these reactions were evaluated as described in Example IV with the following results:

Product: HWT

(5) Decyl diethyl indanylmethyl ammonium chloride 30O (6) Dodecyl diethyl indanylmethyl ammonium chloride 700 (7) Dodecyl dimethyl indanylmethyl ammonium chloride 1100 (8) Tetradecyl dimethyl indanylmethyl ammonium chloride 700 By comparing results obtained using products (2) and (3) from Example IV with products (7) and (8) above, it can be seen that the products derived from idan derived from a commercial source without extensive purification are equivalent to those obtained using highly purified indan. This is significant because it obviates the necessity for expensive and time-consuming purification.

The results of microbiocidal activity, as indicated above, show unexpectedly excellent hard water tolerance of the products of this invention since even the adjacent decyl compounds are significantly inferior in this respect.

Instead of chlorine, other halogens such as bromine and iodine may be used as the anion.

The invention claimed is: 1. A compound having the structure:

References Cited UNITED STATES PATENTS 3/1964 Temple 260567.6 M

OTHER REFERENCES Chemical Abstracts, Subject Index, vol. 56 (1962) p. 89N.

LEON ZITVER, Primary Examiner M. W. GLYNN, Assistant Examiner US. Cl. X.R. 2l064; 260-999 

